CN107651758A - A kind of method that organic fertilizer is prepared using starch wastewater - Google Patents

A kind of method that organic fertilizer is prepared using starch wastewater Download PDF

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CN107651758A
CN107651758A CN201711126145.6A CN201711126145A CN107651758A CN 107651758 A CN107651758 A CN 107651758A CN 201711126145 A CN201711126145 A CN 201711126145A CN 107651758 A CN107651758 A CN 107651758A
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honeycomb
parts
prepared
solution
starch wastewater
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CN107651758B (en
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覃央央
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YINGCHENG SHINDOO CHEMICAL Co.,Ltd.
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Guangxi Nanning Rong Weide Amperex Technology Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C05F17/50—Treatments combining two or more different biological or biochemical treatments, e.g. anaerobic and aerobic treatment or vermicomposting and aerobic treatment
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
    • C05F17/90—Apparatus therefor
    • C05F17/964—Constructional parts, e.g. floors, covers or doors
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/004—Liquid waste from mechanical processing of material, e.g. wash-water, milling fluid, filtrate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse

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  • Fertilizers (AREA)

Abstract

The present invention provides a kind of method that organic fertilizer is prepared using starch wastewater.Starch wastewater is handled using honeycomb reative cell, the special honeycomb reative cell heavy metal ion that flat board can be effectively in non-adsorbed starch waste water up and down；Honeycomb cells structure vertical is sandwiched in flat board up and down, honeycomb locular wall carries out trace to mesoporous silicon material using Western blotting and high performance membrane is prepared, enable mesoporous material specific adsorption protein, the distinctive hole of mesoporous material can improve protein adsorbance, and heavy metal ion also has certain adsorption effect；Make composite bacteria decomposing protein in honeycomb cells using micro- oxygen aeration, protein macromolecule is set to be converted to small molecule, organic matter is converted into humic acid, waste water after processing is used to prepare organic fertilizer, bioactive substance content is high, starch wastewater is effectively purified simultaneously, realizes resource reutilization, has good development prospect.

Description

A kind of method that organic fertilizer is prepared using starch wastewater
Technical field
It is more particularly to a kind of to be prepared using starch wastewater the invention belongs to sewage disposal and organic fertilizer preparing technical field The method of organic fertilizer.
Background technology
Starch wastewater is to produce starch or starch deep processing production by raw material of agricultural product such as corn, potato, wheat, rice Product（Starch sugar, glucose, starch derivatives etc.）Caused waste water, typically belongs to high concentrated organic wastewater, is to cause environment One of primary pollution source of pollution.Starch wastewater major pollutants have suspension（SS）, COD（COD）, ammonia nitrogen（NH3- N）, total nitrogen（TN）And total phosphorus（TP）.Starch wastewater, which contains many, simultaneously protein, but its separation has many difficulties.Mesh There is handle not thorough, high energy consumption, invest the shortcomings of big, operating cost is high for preceding starch wastewater treatment technology, it is difficult to effectively Solve environmental pollution and organic matter serious waste two large problems.
Mesoporous silicon material has the spies such as structured changeability, the exact controllability of hydrolysis condensation reaction and surface modificability Point, prepare for adsorbent for, help to prepare different types of adsorbent the characteristics of silicon-based mesoporous material, to adapt to difference Environmental demand, in addition, mesoporous silicon material be easy to after absorption mother liquor separation, can be real by processes such as pickling, roasting or extractions Existing pollutant resources and adsorbent reactivation.
Molecular imprinting technology be widely used to chromatographic isolation, SPE, Pharmaceutical Analysis, biosensor technology and One of the numerous areas such as catalyze and synthesize, and thus become new field of chemistry and biology intersection, show good Application prospect.Molecular engram is to be polymerize in polymer monomer solution template molecule with crosslinking agent to obtain solid dielectric, Then by either physically or chemically elute remove medium in template molecule, obtain " trace " have target molecule space structure and The molecularly imprinted polymer for having the covalent type compared with high selectivity of binding site（MIPs）.It is contemplated that：A series of function monomers Met in the solution with template molecule, hydrogen bond, electrostatic interaction, hydrophobic effect and other non-covalent can be passed through between them Interaction, make these functional moleculars and arranged to each other with the order state complementary with template molecule structure phase, in work( Covalent complex can be prepared between monomer and template molecule or forms non-covalent addition compound product；By template molecule from polymerization Removed in thing, then in high polymer, the space occupied originally by template molecule forms a cavity left, suitable Under conditions of, this cavity " can satisfactorily remember " the Jie Gou ﹑ sizes of template and other physico-chemical properties, and can effectively and Selectively go be bonded template (or the like) molecule.
Number of patent application CN200910236321.0, trichoderma microbial manure is produced using Sweet Potato Starch Processing Waste Water, with sweet potato Caused waste water is main nutrient raw material in starch production process, and Trichoderma is produced using liquid and the method for solid-state combined ferment Microbial manure has the characteristics of production cost is low, environment-friendly, and product can be obviously improved soil environment quality, improve and make produce Amount, and plurality of plant diseases can be prevented and treated, while be caused a large amount of high concentrations in efficient process sweet potato starch production process Waste water finds effective processing method, reduces environmental pollution.Number of patent application CN201310468266.4, is given birth to using starch wastewater The method for producing liquid organic fertilizer, by addition after the waste water removal of impurity for producing cornstarch or wheaten starch discharge in closed appearance In device, inoculating lactobacillus acidophilus, saccharomyces cerevisiae are fermented, and can effectively mitigate pollution of the waste water to environment by the invention, And can realizes twice laid, and investment is small, and technique is simple, and fertilizer efficiency is notable, and production cost is low, and competitive advantage is strong, test-manufactures potentiality Greatly.Number of patent application CN201610710440.5, liquid organic fertilizer for improveing salt-soda soil is produced using starch wastewater Method, pass through strainer filtering, anaerobic biofilter fermentation, the fermentation of solar energy aeration biofilter, starch phosphate fat and poly- phosphorus chlorine Change a series of advanced treatings such as molten iron solution, microbial fermentation inoculum fermentation so that starch wastewater, which turns into, is rich in beneficial microbe bacterium Group and the liquid microbe fertilizer of a variety of secondary metabolites, secondary salinization of land microbial populations in soil quantity is improved after use and is reduced The problem of, secondary salinization of land volume increase 20% ~ 30% is may be such that, cost is both saved, also alleviates soil depletion, hardened, salinization of soil, Composite energy-saving, environmental protection, the trend of sustainable development.Number of patent application CN201410015439.1, one kind utilize farina Waste water prepares the method that potato leaches powder, by potato starch wastewater first through cleaning, concentrating；Concentrate is then pumped into enzyme Tank is solved, respectively through medium temperature amylase, carbohydrase, neutral proteinase（Or compound protease）Digested three times, then enzyme deactivation；Water Solution product is concentrated again, spray drying, and product is that potato leaches powder.The present invention passes through life using potato starch wastewater Thing engineering means leach powder to produce containing the potato of substantial amounts of amino acid and peptide matters, turn waste into wealth, and cost is cheap, production Product added value is high, there is very huge competitive advantage, while solves starch wastewater improvement and emission problem.
In the prior art, can much have been studied using material technology using biofermentation processing starch wastewater production, but It is that preconditioning technique is complicated in most technology, can not effectively removes the materials such as heavy metal in waste water, while needed during biofermentation Starch wastewater is repeatedly added, labour is big, high energy consumption.With reference to mesoporous material and molecular imprinting technology, starch wastewater is carried out Effectively purify, and the technology for preparing organic fertilizer has no report.
The content of the invention
For technical sophistication existing for starch wastewater treatment method in the prior art, the problems such as effect is low, the present invention provides A kind of method that imitative honeycomb reative cell processing starch wastewater prepared using molecular engram mesoporous material prepares organic fertilizer, passes through Following methods are realized：
A kind of method that organic fertilizer is prepared using starch wastewater, is comprised the following steps：
（1）Prepare imitative honeycomb structure reative cell；
（2）Micro- oxygen aerated conduit is installed in waste water reaction bottom of pond, imitative honeycomb structure reative cell is laid on aerated conduit；
（3）The inoculation fermentation strain in the honeybee room for put honeycomb reative cell, starch wastewater is added in reaction tank I, makes waste water complete Submerge and imitate honeycomb reative cell, after 1 ~ 2d of biological respinse, waste water in reaction tank I is persistently discharged into reaction tank II and carries out biology instead Should, waste water hydraulic detention time in reaction tank II is discharged into reaction tank I after being 8 ~ 10h, after 6 ~ 8d of circular response, stops reaction The circulation and addition of waste water in pond I and reaction tank II, imitative honeycomb reative cell upper flat plate is opened, starch wastewater after discharge fermentation, is added Enter the allotment of nitrogen phosphorus auxiliary material, you can obtain organic fertilizer.
The imitative honeycomb structure reative cell preparation method is as follows：
Honeycomb room is prepared into trace mesoporous material, then honeycomb flat board is prepared into mesoporous silicon material, is then sandwiched in honeycomb room Among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell, each specific preparation process of structure is such as perpendicular to two flat boards Under：
A. the preparation of trace mesoporous material
（1）Under room temperature condition, weigh 2 ~ 3 parts of 3- aminopropyls-triethoxysilanes and 2 ~ 4 parts of template protein solution be dissolved in it is anhydrous Ethanol, the tetramethylammonium hydroxide aqueous solution of 2 ~ 4 parts of mass fractions 25%, obtained solution A is added dropwise；It is meanwhile poly- by 8 ~ 15 parts Ethylene glycol 2000 and 400 ~ 750 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture moves Enter surface plate, place at room temperature until solvent volatilization finishes to obtain product C；
（3）By product C at 60 ~ 80 DEG C 10 ~ 20h of hydrothermal crystallizing, then by product C be placed in 35 ~ 40 DEG C of vacuum drying chambers do Dry 2 ~ 3h, take out and first eluted with 0.1 ~ 0.3mol/L sodium chloride solutions, then flowed back in 60 ~ 70 DEG C of alcohol hydrochloric acid extract 1d obtains trace mesoporous material with removed template method；
B. the preparation of honeycomb room
8 ~ 12 parts of trace mesoporous material is taken, 20 ~ 24 parts of nylon66 fibers is added and is prepared into structural material thin slice, coated in polytetrafluoroethylene (PTFE) Roll on wind, be prepared into honeycomb room；
The nylon66 fiber viscosity is 180 ~ 220g/ml；
The intensity and resilience of the viscosity influence honeycomb room of nylon66 fiber, the honeycomb room for making to be prepared have good anti-pressure ability And heat resistance, reduce in fermentation process under caused heat long term to the illeffects of honeycomb reative cell.
C. the preparation of honeycomb flat board
（1）Under room temperature condition, weigh 2 ~ 3 parts of three-Ethoxysilanes of 3- aminopropyls and 2 ~ 4 parts of modification of chitosan are dissolved in anhydrous second Alcohol, the tetramethylammonium hydroxide aqueous solution of 2 ~ 4 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 8 ~ 15 parts of poly- second Glycol 2000 and 400 ~ 750 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture falls Enter film forming on glass plate, 36 ~ 48h of hydrothermal crystallizing at 90 ~ 100 DEG C, then product is placed in 35 ~ 40 DEG C of vacuum drying chambers and done Dry 2 ~ 3h, take out and first eluted with 0.1 ~ 0.3mol/L sodium chloride solutions, then flowed back in 60 ~ 70 DEG C of alcohol hydrochloric acid extract 1d obtains honeycomb flat board with removed template method；
（3）Honeycomb room is sandwiched among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell perpendicular to two flat boards.
The honeycomb flat board that amination mesoporous silicon material is prepared into, there is good heavy metal ion adsorbed performance and to cause of disease The killing action of bacterium, waste water is permeated by flat board first is entering the progress microbial fermentation reaction of honeybee room, has reached a huge sum of money first Belong to the preliminary removal of ion and kill the effect of pathogen, be that the microbial fermentation in honeybee room improves good reflection environment.
As a further improvement on the present invention, the honeybee locular wall 0.5 ~ 1.5mm of thickness, honeybee room bore are 40 ~ 100mm, honeybee Room 120 ~ 400mm of pipe range, pipe range are 3 ~ 4 with internal diameter ratio；
Honeycomb structure has good anti-pressure ability, in light weight, while honeybee room has the reaction compartment of large area, the wall of honeycomb room The orientation of thick, diameter and honeycomb room tube wall determines the stability of material, and wall thickness and the diameter of honeycomb room determine whole reaction The anti-pressure ability and hydraulic detention time of room, when pipe range and internal diameter ratio are 3 ~ 4, hydraulic detention time can be maintained at 1 ~ 2 My god；The imitative honeycomb structure reative cell that the combination of mesoporous material and molecular imprinting technology is prepared, its distinctive structure have very Good anti-pressure ability, can reduce because waste water stream it is dynamic caused by the effect of Turbulent Flow Effects microbial fermentation, reduce hydraulic pressure and act on to reacting The destruction of room；On the other hand, honeycomb structure can provide microorganism bigger reaction compartment, mesoporous material energy imprinted material energy Specific recognition and adsorbed proteins, mesoporous material have very big specific surface area, make the protein in waste water more more effective Enrichment.
As a further improvement on the present invention, micro- oxygen aerated conduit is snake pipe, and oxygen outlet is managed down, during installation Road and bottom of pond vertical range are 5 ~ 8cm；Dissolved oxygen concentration is 0.3 ~ 0.8mg/L in reaction tank.
In micro- oxygen aeration system, itch bacterium, amphimicrobe and anaerobic bacteria while occurs well, itches compared to simple getting well or anaerobism, More comprehensively, various microorganisms mutually cooperate with microbe species, complete degradation function jointly in micro- foster system.
As a further improvement on the present invention, described fermented bacterium is bacillus megateriumBacillus megaterium, blown-ball AzotobacterAzotobacter chroococcum, aspergillus versicolorAspergillus versicolor, bacillus licheniformisBacillus licheniformisMiddle one or more kinds of combinations；Huge gemma bar Bacterium inoculum concentration is 5% ~ 8%, and cell age is 12 ~ 18h；Blown-ball Azotobacter inoculum concentration is 2% ~ 4%, and kind age is 14 ~ 16h；Aspergillus versicolor connects Kind amount is 4% ~ 6%, and kind age is 12 ~ 16h；Bacillus licheniformis inoculum concentration is 3% ~ 5%, and kind age is 13 ~ 16h.
Bacillus megateriumBacillus megaterium, can be most of in starch-splitting waste water for protein decomposing bacteria Organic matter and protein, while be also organophosphor decomposer, available for manufacturing phosphorous bacterial fertilizer；
Bacillus licheniformisBacillus licheniformisPoisonous and harmful substance in energy starch-splitting waste water, has stronger Protease and amylase activity, Starch Hydrolysis can be promoted, while the bacterium can grow in rugged environment, under the conditions of micro- support Its biological decomposition can be played, material can supply anaerobic nitrogen-fixation bacterium blown-ball Azotobacter and aspergillus versicolor caused by its starch-splitting Growth, while pathogenic bacteria can be killed；
Blown-ball AzotobacterAzotobacter chroococcum, aspergillus versicolorAspergillus versicolorIn micro- foster bar Organic nitrogen material breeding in starch wastewater can be utilized under part, reaches purification of waste water effect, while energy caused by fixed nitrogen process The growth of other microbial reproductions can be supplied.
As a further improvement on the present invention, the template protein solution preparation step is as follows：
A. starch wastewater sample is taken, the filtrate after double-layer filter cloth filtering stands 2h, centrifuges 15min under 6000r/min, take supernatant Liquid, the sodium hydroxide solution that isometric pH is 9 ~ 10 is added, 60min is extracted, then centrifuges 15min under 6000r/min；Take Clear liquid 1；
B. added in supernatant 1 isometric pH be 3 ~ 4.5 hydrochloric acid solution, precipitate 10min, then again under 8000r/min from Heart 15min, precipitation are thick protein；
C., crude protein powder is dissolved in 4 ~ 6ml pH6.2 KH2PO4-NaHPO4In buffer solution, being prepared into protein concentration is 0.15mmol/L solution, after protein is completely dissolved, adds 0.2 ~ 0.5 part of acrylamide and 8 ~ 10h is placed at 4 DEG C；
D. the ammonium persulfate that 180 ~ 200 μ L mass fractions are 10% is added in overnight protein solution, you can obtain template egg White matter solution.
, can be at starch wastewater because its structure is all from same source by the use of starch wastewater protein as template molecule More preferable identification of protein, makes protein-enriched in reason, allows microorganism is more preferably more convenient to be decomposed.
As a further improvement on the present invention, the 3- aminopropyls-triethoxysilane：TMAH：It is poly- Ethylene glycol 2000：Tetraethyl orthosilicate：The mol ratio of absolute ethyl alcohol is 0.20 ~ 0.30：(0.1~0.3)：(0.07~0.1)：1： (50~75).Wherein TMAH：Tetraethyl orthosilicate optimum mole ratio is 0.25:1, (0.1:1)~(0.3:1) scope Interior change.
3- aminopropyl triethoxysilanes provide amido functional group, and tetraethyl orthosilicate provides silicon source synthesizing amino functionalization and is situated between Hole silicon materials, its amido functional group having can be combined with the heavy metal ion in waste water reaches absorption heavy metal ion effect.
Using PEG2000 as template, it is Hydrogenbond between nonionic surface active agent, with silicon source that it, which is, and structure is steady Fixed, in addition, PEG2000 has good compatibility with etoh solvent, long-chain is changed into meander configuration after dissolving, and above feature is to close Created favorable conditions into ordered mesopore structure.
Uniform as mesoporous material pore size distribution$ prepared by surfactant using PEG2000, average pore size is big, heavy metal Absorption property it is excellent.
Co-template supplemented by TMAH, catalyst is can be used as, while can effectively reduce Long carbon chain bending Coiling, hence it is evident that improve mesoporous order and hole diameter enlargement.
Beneficial effects of the present invention：
1st, organic fertilizer is prepared using starch wastewater, does not only reach water treatment effect, while the organic fertilizer viable count produced Amount is high, realizes reutilization of the sewage and organic fertilizer exploitation double benefit；
2nd, the imitative honeycomb reative cell that trace mesoporous material is prepared, special material can adsorb the heavy metal ion in waste water, energy The reaction environment of microbial safety is provided, while mesoporous material more can more effectively identify and collectin matter, makes microorganism more Good decomposing protein.
Brief description of the drawings
Fig. 1 is imitative honeycomb structure reative cell prepared by the present invention, wherein 1 and 2 be honeycomb flat board, 3 be the mesoporous honeycomb of trace Locular wall, 4 be the honeycomb room for providing microbial reaction.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
First, imitative honeycomb structure reative cell is prepared：
A. the preparation of trace mesoporous material
（1）Under room temperature condition, weigh 2 parts of 3- aminopropyls-triethoxysilanes and 2 parts of template protein solution are dissolved in anhydrous second Alcohol, the tetramethylammonium hydroxide aqueous solution of 2 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 8 parts of polyethylene glycol 2000 and 400 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture moves Enter surface plate, place at room temperature until solvent volatilization finishes to obtain product C；
（3）By product C at 60 ~ 80 DEG C hydrothermal crystallizing 10h, then by product C be placed in 35 DEG C of vacuum drying chambers dry 2h, take Go out and first eluted with 0.1 ~ mol/L sodium chloride solutions, the 1d that then flowed back in 60 DEG C of alcohol hydrochloric acid extract with removed template method, Obtain trace mesoporous material；
B. the preparation of honeycomb room
8 parts of trace mesoporous material is taken, the nylon66 fiber that 20 parts of viscosity are 180g/ml is added and is prepared into structural material thin slice, poly- four Wound on the roll of PVF coating, be prepared into that honeybee locular wall thickness is 0.5mm, honeybee room bore is 40mm, honeybee room pipe range is 120mm Honeycomb room；
C. the preparation of honeycomb flat board
（1）Under room temperature condition, weigh 2 parts of three-Ethoxysilanes of 3- aminopropyls and 2 parts of modification of chitosan are dissolved in absolute ethyl alcohol, by It is added dropwise to the tetramethylammonium hydroxide aqueous solution of 2 parts of mass fractions 25%, obtained solution A；Meanwhile by 8 parts of polyethylene glycol 2000s and 400 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 8 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture pours into Film forming on glass plate, the hydrothermal crystallizing 36h at 90 DEG C, then product is placed in 35 DEG C of vacuum drying chambers and dries 2h, is taken out first Eluted with 0.1mol/L sodium chloride solutions, the 1d that then flowed back in 60 DEG C of alcohol hydrochloric acid extract is obtained with removed template method Honeycomb flat board；
（3）Honeycomb room is sandwiched among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell perpendicular to two flat boards.
2nd, micro- oxygen aerated conduit is installed in waste water reaction bottom of pond, imitative honeycomb structure reative cell is laid on aerated conduit； Micro- oxygen concentration in reaction tank is 0.3mg/L.
3rd, in the honeybee room 4 for put honeycomb reative cell inoculation 5% kind age be 12h bacillus megaterium, 3% kind age be The blown-ball Azotobacter that 13h bacillus licheniformis and 2% kind age are 14h, starch wastewater is added in reaction tank I, makes waste water complete Complete submerge imitates honeycomb reative cell upper flat plate 1, after biological respinse 1d, waste water in reaction tank I is persistently discharged into reaction tank II and carried out Biological respinse, waste water hydraulic detention time in reaction tank II is discharged into reaction tank I after being 8h, after circular response 6d, is stopped anti- The circulation and addition of waste water in pond I and reaction tank II are answered, opens imitative honeycomb reative cell upper flat plate 1, discharges starch wastewater after fermentation, It can obtain organic fertilizer；
In the organic fertilizer being prepared into by the present embodiment, total viable count is 1.4 × 108Individual/ml, total amino acid content are 188g/L。
Embodiment 2
First, imitative honeycomb structure reative cell is prepared：
A. the preparation of trace mesoporous material
（1）Under room temperature condition, weigh 3 parts of 3- aminopropyls-triethoxysilanes and 4 parts of template protein solution are dissolved in anhydrous second Alcohol, the tetramethylammonium hydroxide aqueous solution of 3 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 15 parts of polyethylene glycol 2000 and 750 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 12 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture moves Enter surface plate, place at room temperature until solvent volatilization finishes to obtain product C；
（3）By product C at 80 DEG C hydrothermal crystallizing 20h, then by product C be placed in 40 DEG C of vacuum drying chambers dry 3h, take out First eluted with 0.3mol/L sodium chloride solutions, the 1d that then flowed back in 70 DEG C of alcohol hydrochloric acid extract is obtained with removed template method To trace mesoporous material；
B. the preparation of honeycomb room
12 parts of trace mesoporous material is taken, the nylon66 fiber that 24 parts of viscosity are 220g/ml is added and is prepared into structural material thin slice, poly- four PVF coating roll on wind, be prepared into honeybee locular wall thickness be 1.5mm, in honeybee room footpath be 100mm, honeybee room pipe range be 400mm Honeycomb room；
C. the preparation of honeycomb flat board
（1）Under room temperature condition, weigh 3 parts of three-Ethoxysilanes of 3- aminopropyls and 4 parts of modification of chitosan are dissolved in absolute ethyl alcohol, by It is added dropwise to the tetramethylammonium hydroxide aqueous solution of 4 parts of mass fractions 25%, obtained solution A；Meanwhile by 15 parts of polyethylene glycol 2000s Mixed with 750 parts of absolute ethyl alcohols, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture falls Enter film forming on glass plate, the hydrothermal crystallizing 48h at 100 DEG C, then product is placed in 40 DEG C of vacuum drying chambers and dries 3h, is taken out First eluted with 0.3mol/L sodium chloride solutions, the 1d that then flowed back in 70 DEG C of alcohol hydrochloric acid extract is obtained with removed template method To honeycomb flat board；
（3）Honeycomb room is sandwiched among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell perpendicular to two flat boards.
2nd, micro- oxygen aerated conduit is installed in waste water reaction bottom of pond, imitative honeycomb structure reative cell is laid on aerated conduit； Micro- oxygen concentration in reaction tank is 0.8mg/L.
3rd, the bacillus megaterium that 8% kind of age is 18h is inoculated with the honeybee room for put honeycomb reative cell, 3% kind of age is 16h's The aspergillus versicolor that bacillus licheniformis and 6% kind of age are 16h, starch wastewater is added in reaction tank I, is totally submerged waste water imitative Honeycomb reative cell, after biological respinse 2d, waste water in reaction tank I is persistently discharged into reaction tank II and carries out biological respinse, waste water exists Hydraulic detention time is discharged into reaction tank I after being 8 ~ 10h in reaction tank II, after circular response 8d, stops reaction tank I and reaction tank The circulation and addition of waste water in II, open imitative honeycomb reative cell upper flat plate, starch wastewater after discharge fermentation, you can obtain organic fertilizer Material；
In the organic fertilizer being prepared into by the present embodiment, total viable count is 1.3 × 108Individual/ml, total amino acid content are 182g/L。
Embodiment 3
First, imitative honeycomb structure reative cell is prepared：
A. the preparation of trace mesoporous material
（1）Under room temperature condition, weigh 2.3 parts of 3- aminopropyls-triethoxysilanes and 3 parts of template protein solution are dissolved in anhydrous second Alcohol, the tetramethylammonium hydroxide aqueous solution of 2.5 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 8 parts of poly- second two Alcohol 2000 and 500 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture moves Enter surface plate, place at room temperature until solvent volatilization finishes to obtain product C；
（3）By product C at 64 DEG C hydrothermal crystallizing 18h, then by product C be placed in 38 DEG C of vacuum drying chambers dry 3h, take out First eluted with 0.2mol/L sodium chloride solutions, the 1d that then flowed back in 68 DEG C of alcohol hydrochloric acid extract is obtained with removed template method To trace mesoporous material；
B. the preparation of honeycomb room
10 parts of trace mesoporous material is taken, the nylon66 fiber that 22 parts of viscosity are 200g/ml is added and is prepared into structural material thin slice, poly- four Wound on the roll of PVF coating, be prepared into honeybee locular wall thickness 1mm, honeybee room bore is 60mm, honeybee room pipe range 240mm honeycomb Room；
C. the preparation of honeycomb flat board
（1）Under room temperature condition, weigh 2.3 parts of three-Ethoxysilanes of 3- aminopropyls and 4 parts of modification of chitosan be dissolved in absolute ethyl alcohol, The tetramethylammonium hydroxide aqueous solution of 2.5 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 8 parts of polyethylene glycol 2000 and 500 parts of absolute ethyl alcohols mix, obtained solution B；
（2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture falls Enter film forming on glass plate, 36 ~ 48h of hydrothermal crystallizing at 88 DEG C, then product is placed in 40 DEG C of vacuum drying chambers and dries 3h, is taken Go out and first eluted with 0.2mol/L sodium chloride solutions, the 1d that then flowed back in 66 DEG C of alcohol hydrochloric acid extract with removed template method, Obtain honeycomb flat board；
（3）Honeycomb room is sandwiched among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell perpendicular to two flat boards.
2nd, micro- oxygen aerated conduit is installed in waste water reaction bottom of pond, imitative honeycomb structure reative cell is laid on aerated conduit； Micro- oxygen concentration in reaction tank is 0.6mg/L.
3rd, the bacillus megaterium that 6% kind of age is 14h is inoculated with the honeybee room for put honeycomb reative cell, 3% kind of age is 15h's Blown-ball Azotobacter, the bacillus licheniformis that the aspergillus versicolor and 4% kind of age that 5% kind of age is 14h are 14h, starch wastewater is added anti- Answer in pond I, waste water is totally submerged imitative honeycomb reative cell, after biological respinse 2d, waste water in reaction tank I is persistently discharged into reaction tank Biological respinse is carried out in II, waste water hydraulic detention time in reaction tank II is discharged into reaction tank I after being 10h, circular response 8d Afterwards, stop the circulation and addition of waste water in reaction tank I and reaction tank II, imitative honeycomb reative cell upper flat plate is opened, after discharge fermentation Starch wastewater, you can obtain organic fertilizer；
In the organic fertilizer being prepared into by the present embodiment, total viable count is 1.8 × 108Individual/ml, total amino acid content are 192g/L。
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair The equivalent transformation that bright description is done, or other related technical areas are directly or indirectly used in, similarly it is included in In the scope of patent protection of the present invention.

Claims (7)

  1. A kind of 1. method that organic fertilizer is prepared using starch wastewater, it is characterised in that comprise the following steps：
    （1）Prepare imitative honeycomb structure reative cell；
    （2）Micro- oxygen aerated conduit is installed in waste water reaction bottom of pond, imitative honeycomb structure reative cell is laid on aerated conduit；
    （3）The inoculation fermentation strain in the honeybee room for put honeycomb reative cell, starch wastewater is added in reaction tank I, makes waste water complete Submerge and imitate honeycomb reative cell, after 1 ~ 2d of biological respinse, waste water in reaction tank I is persistently discharged into reaction tank II and carries out biology instead Should, waste water hydraulic detention time in reaction tank II is discharged into reaction tank I after being 8 ~ 10h, after 6 ~ 8d of circular response, stops reaction The circulation and addition of waste water in pond I and reaction tank II, imitative honeycomb reative cell upper flat plate is opened, starch wastewater after discharge fermentation, is added Enter rich Nitrogen-and Phosphorus-containing auxiliary material to be allocated, you can obtain organic fertilizer；
    The imitative honeycomb structure reative cell preparation method is as follows：
    Honeycomb room is prepared into trace mesoporous material, then honeycomb flat board is prepared into mesoporous silicon material, is then sandwiched in honeycomb room Among honeycomb flat board, honeycomb room is assembled into imitative honeycomb structure reative cell, each specific preparation process of structure is such as perpendicular to two flat boards Under：
    A. the preparation of trace mesoporous material
    （1）Under room temperature condition, weigh 2 ~ 3 parts of 3- aminopropyls-triethoxysilanes and 2 ~ 4 parts of template protein solution be dissolved in it is anhydrous Ethanol, the tetramethylammonium hydroxide aqueous solution of 2 ~ 4 parts of mass fractions 25%, obtained solution A is added dropwise；It is meanwhile poly- by 8 ~ 15 parts Ethylene glycol 2000 and 400 ~ 750 parts of absolute ethyl alcohols mix, obtained solution B；
    （2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture moves Enter surface plate, place at room temperature until solvent volatilization finishes to obtain product C；
    （3）By product C at 60 ~ 80 DEG C 10 ~ 20h of hydrothermal crystallizing, then by product C be placed in 35 ~ 40 DEG C of vacuum drying chambers do Dry 2 ~ 3h, take out and first eluted with 0.1 ~ 0.3mol/L sodium chloride solutions, then flowed back in 60 ~ 70 DEG C of alcohol hydrochloric acid extract 1d obtains trace mesoporous material with removed template method；
    B. the preparation of honeycomb room
    8 ~ 12 parts of trace mesoporous material is taken, 20 ~ 24 parts of nylon66 fibers is added and is prepared into structural material thin slice, coated in polytetrafluoroethylene (PTFE) Roll on wind, be prepared into honeycomb room；
    The nylon66 fiber viscosity is 180 ~ 220g/ml；
    C. the preparation of honeycomb flat board
    （1）Under room temperature condition, weigh 2 ~ 3 parts of three-Ethoxysilanes of 3- aminopropyls and 2 ~ 4 parts of modification of chitosan are dissolved in anhydrous second Alcohol, the tetramethylammonium hydroxide aqueous solution of 2 ~ 4 parts of mass fractions 25%, obtained solution A is added dropwise；Meanwhile by 8 ~ 15 parts of poly- second Glycol 2000 and 400 ~ 750 parts of absolute ethyl alcohols mix, obtained solution B；
    （2）After reacting 2h, A, B solution are sufficiently mixed, then 10 parts of tetraethyl orthosilicates are added dropwise, and are slowly stirred 1h；Mixture falls Enter film forming on glass plate, 36 ~ 48h of hydrothermal crystallizing at 90 ~ 100 DEG C, then product is placed in 35 ~ 40 DEG C of vacuum drying chambers and done Dry 2 ~ 3h, take out and first eluted with 0.1 ~ 0.3mol/L sodium chloride solutions, then flowed back in 60 ~ 70 DEG C of alcohol hydrochloric acid extract 1d obtains honeycomb flat board with removed template method.
  2. A kind of 2. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：Described Nitrogen phosphorus auxiliary material is one kind in wheat bran, dregs of beans；Waste water is calculated after being fermented by 1L, adds 200 ~ 400g wheat brans or 100 ~ 300g dregs of beans enters Row allotment.
  3. A kind of 3. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：Honeybee locular wall 0.5 ~ 1.5mm of thickness, honeybee room bore are 40 ~ 100mm, and honeybee room 120 ~ 400mm of pipe range, pipe range is 3 ~ 4 with internal diameter ratio.
  4. A kind of 4. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：It is described anti- Ying Chizhong dissolved oxygen concentrations are 0.3 ~ 0.8mg/L.
  5. A kind of 5. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：Described Fermented bacterium is bacillus megateriumBacillus megaterium, blown-ball AzotobacterAzotobacter chroococcum、 Aspergillus versicolorAspergillus versicolor, bacillus licheniformisBacillus licheniformisMiddle one kind or one Kind combination of the above；Bacillus megaterium inoculum concentration is 5% ~ 8%, and cell age is 12 ~ 18h；Blown-ball Azotobacter inoculum concentration is 2% ~ 4%, kind Age is 14 ~ 16h；Aspergillus versicolor inoculum concentration is 4% ~ 6%, and kind age is 12 ~ 16h；Bacillus licheniformis inoculum concentration is 3% ~ 5%, kind Age is 13 ~ 16h.
  6. A kind of 6. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：The mould Plate protein solution preparation process is as follows：
    A. starch wastewater sample is taken, the filtrate after double-layer filter cloth filtering stands 2h, centrifuges 15min under 6000r/min, take supernatant Liquid, the sodium hydroxide solution that isometric pH is 9 ~ 10 is added, 60min is extracted, then centrifuges 15min under 6000r/min；Take Clear liquid 1；
    B. added in supernatant 1 isometric pH be 3 ~ 4.5 hydrochloric acid solution, precipitate 10min, then again under 8000r/min from Heart 15min, precipitation are thick protein；
    C., crude protein powder is dissolved in 4 ~ 6ml pH6.2 KH2PO4-NaHPO4In buffer solution, being prepared into protein concentration is 0.15mmol/L solution, after protein is completely dissolved, adds 0.2 ~ 0.5 part of acrylamide and 8 ~ 10h is placed at 4 DEG C；
    D. the ammonium persulfate that 180 ~ 200 μ L mass fractions are 10% is added in overnight protein solution, you can obtain template egg White matter solution.
  7. A kind of 7. method that organic fertilizer is prepared using starch wastewater according to claim 1, it is characterised in that：The 3- Aminopropyl-triethoxysilane：TMAH：Polyethylene glycol 2000：Tetraethyl orthosilicate：Absolute ethyl alcohol mole is matched somebody with somebody Than for (0.20 ~ 0.30)：(0.1~0.3)：(0.07~0.1)：1：(50~75).
CN201711126145.6A 2017-11-15 2017-11-15 Method for preparing organic fertilizer by using starch wastewater Active CN107651758B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845078A (en) * 2010-04-14 2010-09-29 兰州大学 Method for extracting protein from wastewater of potato starch
CN102616794A (en) * 2012-04-11 2012-08-01 宣城晶瑞新材料有限公司 Preparation method for high-dispersibility nanometer silicon dioxide
CN102815795A (en) * 2012-09-12 2012-12-12 广西民族大学 Method for processing starch wastewater as well as product and application thereof
JP2014008474A (en) * 2012-06-29 2014-01-20 Matsumoto Yuki Pond water circulation hybrid purification method and pond water circulation hybrid purification system
WO2016126596A2 (en) * 2015-02-06 2016-08-11 Cabot Corporation Urea sequestration compositions and methods
CN106316690A (en) * 2016-08-24 2017-01-11 山东胜伟园林科技有限公司 Method for produce liquid organic fertilizer with starch wastewater to improve saline and alkaline land

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845078A (en) * 2010-04-14 2010-09-29 兰州大学 Method for extracting protein from wastewater of potato starch
CN102616794A (en) * 2012-04-11 2012-08-01 宣城晶瑞新材料有限公司 Preparation method for high-dispersibility nanometer silicon dioxide
JP2014008474A (en) * 2012-06-29 2014-01-20 Matsumoto Yuki Pond water circulation hybrid purification method and pond water circulation hybrid purification system
CN102815795A (en) * 2012-09-12 2012-12-12 广西民族大学 Method for processing starch wastewater as well as product and application thereof
WO2016126596A2 (en) * 2015-02-06 2016-08-11 Cabot Corporation Urea sequestration compositions and methods
CN106316690A (en) * 2016-08-24 2017-01-11 山东胜伟园林科技有限公司 Method for produce liquid organic fertilizer with starch wastewater to improve saline and alkaline land

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